Process of reforming hydrocarbons



Patented Dec. 30, 1947 PROCESS OFJREFORMING HYDROCARBONS Jacquelin E.Harvey, J1'.,Washington, D. 0., and Robert H. White, Jr., and Joseph A.Vaughan, Atlanta, Ga., asst'gnors of one-half to Jacquelin E. Harvey,Jr., Washington, D. 0., and onehalf to SouthernWood Preserving Company,East Point, Ga., a corporation of Georgia No Drawing. ApplicationOctober 7, 1944,

7 Serial No. 557,724

The instant invention relates to the production of toxic oils employableas fungicides, insecticides, and for any other service to which toxicoils may be put.

This application is a continuation-in-part of our application Serial No.467,416, filed Novem ber 30, 1942, for Method of providing a new oil,copending herewith, and which is now abandcned, as to allmatter commonto the two applications.

More especially the instant invention relates to the production of toxicoils from mixtures of petroleum fractions characterized by ringstructure content. Among such starting materials may be mentionedmixtures of petroleum fractions characterized by ring structure contentre covered from petroleum fractions by well known extraction methodsincluding extractive distillation and solvent extraction. Also may bementioned mixtures of petroleum fractions characterized by ringstructure content as flowing from thermal and/or catalytic treatment ofcertain petroleum fractions which includes petroleum fractions havingring structures induced in the course of thermal and/or catalytictreatment, as for example having ring structures induced in the courseof one or more thermal and/or catalytic treatments of unusual length, asfor example; for periods of from 1-10 hours or more.

An object of the instant invention is the production of toxic oils fromthe aforenamed pctroleum fractions or others whereby to provide oils ofthe preservative type, as for example preservative wood impregnantsconforming to specifications extant or acceptable to the trade con-- Yetanother object of the instant invention isv the provision in the overallbeneficiated material cf t at percentage of newly induced fractions boling below 210 C. which is conducive to the inchiction of toxicity inother fractions-of the material under treatment. 4 Jv l 9 Claims. (01.196-49) Another object of the instant invention is the induction ofadditional toxicity into fractional parts of the oncebeneficiated'startingmaterial under specific controls of processvariables.

A specific object of the invention is the transformation, reformation;conversion and/ or modification of relatively high boiling petroleumoils characterized by structures of cyclic structure content havinginherent but inhibited toxicity whereby to provide said structures ofcyclic structure content as materials exhibitinga more pronounced toxicvalue.

Still another object of the present invention is the conversionofsubstantially non-toxic petroleum type aromatics into materials moreclosely approaching the highly toxic coal tar aromatic type, as morefully set forth in the followingf p Still 'ano therobject of thepresentinvention is the conversion of petroleum type aromatic materialolf a relatively narrow boiling range into materialof relatively wideboiling range more closely approaching the characteristicsof coal tararomatics, by a process wherein the control isevidenced by thepercentage of newly formed aromatics found in certain fractions of thebeneficiat'ed material.

In the past "wood preservative oils of the high temperature coal tarderived type have been employed in quantities greatly exceeding thetotal of all other wood preservative oils. From the standpoint ofavailability of said coal tar as the parent product of wood preservativeoils, it is annually produced in this country under normal conditions tothe extent of five hundred million to six hundred million gallons. Thisquantity of coal tar is capable of yielding an amount of highly.effective wood preservative oil which would make this country selfsufficient in its wood preservative requirements. However, due to thefact that when a Wood preservative distillate (creo sote) is recoveredfrom coal tar there remains in the still a residue (pitch) which, atbest, is a low priced product and which, at worst, is a seriouslydistress product tothe end that at times been imported into-this-eountry.- That such a situation should obtain is apparently aparadox in that we annually produce a quantity of high temperature coaltar which if processed to yield creosote would make us selfsuflicientin. that requirement. A survey of this paradox isfully'outlined in an address given by no less an authority than S. P.Miller, technical director, The Barrett Company, 40 Rector Street, NewYork city, be

fore the Franklin Institute;.Philadelphial'Penn sylvania. in December,1932. n The economics of coal tar have not materially changed: ince thatdate. ;I I I In view of the apparent inability r the eel tar industry toprovide national needs of wood preservative oils, a strong incentiveg'isgivenito groups processing other types of. oil to invade tl e lucrativewood preservative market. At the 'pres: ent time many types of aromaticoils are produced by the petroleum industry, and the high-boilingdils ofaromatic content produced by this industry have for several years beentested for their .wood preservative efficiency. i By-the term petroleumaromaticfas used herein and in the appended claims is meant to includemixtures of petroleum-fractions characterized by cyclic content andincludes specifically various forms and types of naphthenes found invarious mixtures of petroleum fractions, as for example monocyclic andpolycyclic naphthenes.

The so-called petroleum aromatics; whichineludes the monocyclic andpolycyclic naphthenes and. unsaturated cyclic hydrocarbon fractions havein the past been produced in very large guan- In the foregoing tabulardata P. M. C. C. means Pensky-Martin Closed Cup; C. O. C. meansCleveland Open Cup.

Upon evaluating the foregoing oil for its toxicity to wood destroyingfungi (Madison 517), it was found that this oil did not totally inhibitthe growth of the fungi named at a concentration of up to and includingMadison 517 is a strain 'of therungus Fomes ahnosus.

It is nowdiscovered that the oil above named or other oils of .cyclicstructure content produced tities. However, very little work has beendone on these materials. Such a fact'isborne outon page 667, fReactionsof Purel Hydrocarbons, Gustav Egloff," Reinhold Publishin i Corporation,330 West 42nd Street, New York city, whichstates Despite the fact thatnaphthenes orcycloparafiines are available in enormous quantities} asshown by an estimate of 100,000,000 barrels present in the 1.498,000,000barrels of crude oil which was the worlds production in 1934,comparatively little work ofapyrolytic nature has been performed onindividual naphthene hydrocarbons'or the cycloolefins. i Q Several oilsof cyclic content produced by the petroleum industry have been inspectedfor their toxicity to .wooddestroying fungi, amongfwhich may bementioned a high boiling.v oil .of .cyclic structure contentproduced(1940).at the Wood River Refinery of the Shell Oil Company. and whichhas the following inspection:

Gravity Flash, P.-M. 0.0., "F 295 Flash; C; O. C., F 290 Fixed carbon,per cent 4 9 Pour point, F 1 10 B.S:& W. by VO1 4; 0.1 S. U. -Vis. 100 F151 S. U. Vis. 210 F; 41 Vis; 77 F 3415 Carbon residue 6.8 Per; centaromatics and unsaturate 82.4 801. in CS2 V 99.8 Loss 50 grams. 5 hours325 F 8.9 Residue of 100 pene., per cent 37.5 A. S. T. M. distillation:H

I. B. R, F 518 10% Rec. F 565 20% Rec. F 589 Rec. F 614 v 40% Rec. F 637Rec. F 660 60% Rec.-@;F max .675

by thepetroleum industry can be increased in toxfi'eity' accordance withthe process of the instant invention.

According to the instant invention oils of cyclic structure contentproduced by the petroleum industry are reformed, transformed, modifiedand/0r converted to oils of a more toxic nature havingcharacteristicsacceptable to consumers of wood preservative impregnant and/orconforming to wood preservative specifications extant.-

We have discovered that if the starting materials named are subjected toa thermal treatment at a temperature of 325550 C., and if the treatmentis so controlled as to provide in the materials of the end productboiling between 210 C.- and 355 C. a percentage of aromatics notsubstantially less than about 70%, the reformed, converted and/ormodified oil boiling between about 210 C. and 355 C. will have atoxicity to wood destroying fungi approaching or equalling the toxicityof high temperature coal tar or its derivatives, provided (1) thespecific gravities of the overall fractions within the 210-355 C. cut ofthe beneficiation fall about within the limits shown; in the appendedtabular data:

Fractions Low Limit High Limit Or- (2) the specific gravities of thearomatics in the; fractions of the 210-355 C. out of the beneficiatedmaterial fall about within the limits shown in the appended tabulardata:

The-followingexamples will serve to illustrate several modes ofpracticing the present invention.

Example 1.-A mixture of petroleum fractions characterized by asubstantial content of petroleum type aromatics and having but slightgrowth inhibition to wood destroying fungi, as for example, the Shellproduct shown in the foregoing tabular data, is charged to a highpressure autoclave and brought up to a temperature of 500 C. where it isheld for a period of 30 minutes. The pressure reaches a maximum of 1275pounds per square inch. The beneficiated material is cooled andinspected, and is found to have (1) newly formed materials boiling below210 C., and (,2) an overall toxicity approaching or equallingthetoxicity'of certain high temperature coal tar wood preservatives.

Inspection of the beneficiated material discloses mattersshown in theappended tabular data:

All four fractions about 0.50.

The total inhibition point (toxicity test) above noted is expressed asthe percent of the preservae tive by weight of medium on which testedand required to totally inhibit the growth of the fun-' gus under test.The toxicity test isqfully de-= scribed on pages 34 to 43 of the 1933Proceedings of The American Wood Preservers Association.

The Shell oil which was the starting material of the present example hadan unsatisfactory toxicity to wood destroying fungi due to the toxicitydiluents that were attached .to the aromatics, which toxicity diluentsfor working purposes may be considered the side chains attachedto thering nuclei. We have found by controlling the process variables as toprovide in the 210-355 C. out of the beneficiated material (.1) specificgravities in aromatics in fractional parts of said out which fallbetween the limits previously stated, and/or (2) specific gravities inoverall fractions of thenamed out which fall between the limits named inthe foregoing, that this is a guarantee of, and a test for, theinduction of toxicity to wood destroying fungi in the named beneficiatedout which approaches orequals thetoxicity of certain high temperaturecoal tars or theirpreservative derivatives. The controls above named,either or both, are practices by which sufficient toxicity diluents maybe removed from the highly toxic ring nuclei to insure acceptabletoxicity to the wood preserving industry.

By processing the Shell oil in the manner above named, a crude materialwhose total inhibition point to the growth of wood destroying fungi wasin excess of is at least partially converted into a material whichapproaches or equals the toxicity of conventional coal tar creosote.

The beneficiated material is fractionated to recover a wood preservativeimpregnant of induced toxic properties having 2% distilling below 10 0.,more than 1.5% distilling above 315 0. and residue above 355 C. It is ofespecial importance that the newly formed preservative oil has at leastabout -20% residue above 315 C. for it is on these high boilingfractions, among others, that our new oil depends for its permanency.

The materials of induced toxic properties as flowing from the processcarried out under the controls above disclosed have at times substantialresidual matter above 355 0. and may be used in toto as a woodpreservative, or in the event it is desired to provide a woodpreservative impregnant complying with specifications extant or ofconsumer preference, a wood preservative may be segregated from theoverall beneficiated oil as a stabilized residual, distillate orextract, and in the event the extract has non-permissible low boilingends, the extract may be stabilized to the desired necessar extent byremoval of low ends,

As illustrative of wood preservative impregnants of the oil derived typethat have met with consumer acceptance .and which may be segregated fromthe overall beneficiated material of the in tani process. t followingtabu de ention Woon PRESERVATIVE IMPREGNANTS Specifications 1. AmericanWood Preservers Association a. Up to 210 0., not more than 5% a b. Up to235 0., not more than 25% 2.- American Wood Preservers Association a 0..Up to 210 0., not more than 1% 17. Up to 235 0., not more than 10% 0. Upto 355 0., not less than 3. 1 American Wood Preservers Association a. Upto 235 0., not more than 1 b. Up to 300 0., not more than Mi 0. Up to355 0., not less than 45% 4. American Wood Preservers Association 0.. Upto 210 0., not more than 8% r a b. Up to 235 0., not more than 35% 5.American Wood Preservers Association a. Up to 210 0., not more than 10%b. Up to 235 0., not more than 40% 6. American Wood Preservers'Association (1. Up to 210 0., not more than 5% 1). Up to 235 0., notmore than 15% 7. Prussian Ry.

' 0.. Up to 150 0., not more than 3% 5. Up to 200 0., not more than 10%.c. Up to 235 0., not more than 25% 8; National Paint Varnish 8; LacquerAssociation #220 i a. 5% at 162 C. b. 97%at 270 0. '9. Southern PineShingle Stain Oil 0.. 5% at 137 C. I b. at 257 0. Neville Shingle StainOil a. LE. P., 150 C. t. 5% at 205 0. c. 95% at 292 0. v 11. Carbolineum270 0., I. B. P.

I Example 2.--A .petroleum aromatic oil having 4% of low ends below 2350., and boiling preponderantly between 235 0. and 355 0. is

'The 210-355 C. out of the treated oil has the fo lowing inspection:

- on npeci c Percen age hibition Gravity of of Aromatics Point) FractionA.ll four fractions 0.050.

.a'I'he 210-355 0. fraction of the beneficiation issegregated therefromby fractional distillation to provide a highly toxic preservative woodimpregnant as a distillate.

By providing in the beneficiated material the overall specific gravitiesnoted in fractional parts of the 210-355 C. out, a guarantee is securedthat su llicient reforming, cracking, modifying and/or qpnrsrtir bas e ao s e to ns r he 7 materlals 'boiling' betw een"210 C. and 355 C. havinga toxicity comparing favorably with that found in high temperature coaltar wood preservatives.

Example 3.When processing the starting material as disclosed in Examples1 and 2, it is found that the materials boilingbelow and abov 270 C.have a relatively high-and low toxicity, respectively. It is of especialimportance that the materials boiling above 270 C. have as'high atoxicity as possible for the reasorrthat these materials have a toxicityblanketing effect on the lower boiling materials of highest toxicity. Wehave discovered that by retreating the once processed materials boilingabove 270 C. that additional toxicity may be induced. A typical practiceof this phase of our'invention is hereinafter outlined.

The'starting material is subjected to a temperature of 480 for a periodof 45 minutes while maintaining apressure of 750 pounds per square inch.The beneficiated material is cut at 270 C. to'provide 'a low boilingportion of relatively high-toxicityand a high boiling portion ofrelatively lowtoxi,cit-y.- The high boiling portion is subjected to atemperature of 475 C. for a period of 30 minutes at the pressure abovenamed. The onceand-twic treated materials are commingled' and are foundto :have inthe materials boiling between210 (Land 355C. a'percentage ofaromatics in excess of 70%. The specific gravities of the aromatics inquestion fall between the limits shown in foregoing tabular :data, andthe specific gravities ofoverallafractions-in the 210- 355 C. out fallwithin thelimits previously noted. A wood preservative impregnantboilingpreponderantly between 210 (band-355 G. and with 25% residue above 315C. is-segregated from the commingled benefication; and subsequentinspection reveals the fact that it has a-toxicity acceptable to thewood preserving industry, that is to say, a toxicity closely approachingthat found in high temperature coal tar wood preservatives.

. Instead of cutting the primary benefication at 270 C., the cut may bemade at other temperatures, say at 285 0., 300 C. or above. The highboiling portion is then treated at a temperature falling within thdisclosed limits.

We have found when practicing a two-step process as disclosed in theinstant example that by providing a total treatment period. of not inexcess of about two hours, acceptable toxicity approaching or equallingthat of high temperature coal tar preservative products, may beprovided.As illustrative of this mode of practice, a period rYot'ifixcess of onehour may be employed in the primary step, and a period not in excess of30' or 40 minutes, more or less, may be employed in the secondary stepwhich retreats the higher boiling segregation. Such treatment periodshave been found to give the desired results, although other periods oftreatment for the two steps, the total of which falls below about twohours, may be practiced.

Example 4.-A petroleum aromatic oil distilling 3% below 270 C. and with50% residue above 355 C., having an aromatic and unsaturated content ofover 70%, a specific gravity of aromatics of 1.0166 in the 270-315 C.fraction and a specific gravityof aromatics of 1.0256 in th 315-355 C.fraction is subjected to a temperature of 460 C. while under a pressureof 1000 pounds per square inch for a period of one hour. Thereafter theheat treated material, without substantially lowering the-temperature,is held under a pressure of 400 pounds per square inch for a period of30 minutes. At the end of the named second period the benefication iscooled and inspected and is found to have in excess of 70% aromatics inthe materials boiling between 210 C. and 355 C., and the fractionalparts of the 210-355 C. out have aromatics whose specific gravities fallwithin the limits noted in the tabular data previously shown.

The benefication which has newly induced fractions boiling below 210 C.is fractionally distilled to provide a distillate of the woodpreservative type boiling substantially between 210 C. and 355 C. Atoxicity evaluation of the wood preservative type distillate shows thatits toxicity closely approaches that of high temperature coal tarcreosote.

In the two-step operation disclosed in the instant example we have foundthat a period of not in excess of about one hour is suitable for theprimary step. Dependent upon the temperature selected within the rangeherein disclosed, periods of 20, 30 or 40 minutes, more or less, areacceptable. In the secondary step of this mode of practicing the instantinvention, we have found that a period not in excess of about one houris sufficient to induce the desired qualities. When employing in thefirst stage a relatively high temperature Within the range hereindisclosed, and a relatively high pressure drop in the second stage, arelatively short period of treatment in the second stage will providethe desired percentage and specific gravity of aromatics.

. The relationship of the high and low pressure steps may vary overrelatively broad limits, as for example, the first step may be carriedout at Very high pressures and the second step at a pressure onlyslightly above atmospheric. On the other hand, if a relatively lowpressure is employed in the first and high pressure step, say a pressureof about 300 pounds per square inch, then atmospheric or sub-atmosphericpressure may be employed in the second step.

Viewed broadly, this phase of practice of our invention is notcircumscribed by any definite pressures in the high and low pressuresteps, but rather turns on employing a relatively high pressure in thefirst stage and a relatively low pressure in the second stage.

Example 5.The Shell petroleum aromatic oil noted'previously is subjectedto a, temperature of 465 C. 'at a pressure of 900 pounds per square inchfor a period of 40 minutes. Thereafter the partially beneficiatedmaterial is subjected in entirety to a temperature of 500 C. for aperiod of 20 minutes. The beneficiated material is cooled and inspectedand is found to have newly formed fractions boiling below 210 C., and inthe materials boiling between 210-355 C. in excess of aromatics. Thespecific gravity of aromatics in fractional parts of the 210-355 C. outof the beneficiation fall between the limits noted in the tabular datapreviously shown. A toxicity evaluation of the materials boiling between210-355" C. indicate that only about 0.5% is required for totalinhibition of growth of wood destroying fungi.-

We have found that when practicing our invention with a relatively lowtemperature step and a subsequent relatively high temperature step, thetemperatures in both steps being selected between the limits of about325-550 C., optimum conditions are secured by providing a period oftreatment in each step of not in excess of about one hour; Ifrelatively" high temperatures'within the limits named are employed inthe twostep process of dissimilartemperatures; relatively short periodsin the two steps are possible; and we have found that under Very severethermal conditions within the limits named, periods of 10, or minutes ineach step mice to induce the desired characteristics.

Viewed broadly, this phase of our invention is not circumscribed by anydefinite time period, other than the upper limit, but rather turns onthe correct coordination of a relativelylow temperature step and arelatively high temperature step, whereby to provide the desiredpercentage and specific gravity of aromatics and/or desired percentageof aromatics and specific gravity" of overall fractions in the endproduct, which thing or things in turn insure induction of toxicity approaching or equalling that of high temperature coal tar WOOd'preservative impregnants.

When treating certain mixtures of petroleum fractions that have arelatively low petroleum aromatic content we have found the operationalprocedure as outlined in the following exampleof especial merit.

Example 6.A recycle oil containing'lesst than 30%, petroleum aromaticsis sublectedto' the processing conditions disclosed in Example: 1. Uponinspection of, the beneficiated. material it. is found that although thespecific gravity of; the aromatics fall within the limits previouslydisclosed, the total percentage of aromatics is less than 70 Thebeneficiated material is then extractedwith liquid sulfur dioxide andtherafiinate discarded. The extract isthen stabilized to provide aresidual as an oil of the wood preservative type boiling preponderantlybetween2lQ-355jC and whichhas an overall total inhibition point to thegrowth of wood destroying fungi of. not in excess of about 0.5%.

Although liquid sulfur dioxide is shown as the extracting agent, itis-immediately obvious that other materials may be employed, as-forexample furfural or the like. p

Instead of practicing the process in a once through treatment asdisclosed in Example 1, especial toxicity induction benefits flowfromdividing the beneficiation into-arelatively low boiling portion and arelatively high boilingportion; and subsequently retreating separatelythe two fractions. Thetwo fractions may be, treated at similar ordissimilar temperatures within the range previously disclosed. When theyretreated fractions are commingled, it will be foundthat they have atoxicity in excess of the oncetreated material. t t h e In lieu ofretreating both the high and low boiling portion, the low boilingportion may' be retreated and then commingled with the once treated highboiling portion to provide a comminglement having a toxicity in excessofthe once treated'oil.

Another mode of practicing our invention re sides in treating thepetroleum aromatic? containing oil in the presence of benzene; toluene;

thenpior example, treated asuin, Example 1;. The;

resultant alkylatedbenzene is then removed; Upon inspection, it will befound that the petro leumaromatic has a percentage of aromatics notlower than 70% and the specific" gravityof the aromatics in fractionalpart of the 210-355 G:

v 10 cut fall betweenthe limits noted in the tabular datapreviouslyshown. The commingling of parts of the petroleum aromatic with50 parts of benzeneisfor purposes of illustration only; otherpercentages maybe used; When the feedstock consists of a; petroleum oilhaving a;v relatively lowpercentage of petroleum aromatics andunsaturates, it is advisable to first extract the on and thentreataccording to any of the modes or practicing our process;

Example 7; Wehave found indications that the basic-reason whypetroleumaromatic have relatively littletoxicityis becauseoi the relative- 1y"non-toxic materials (side chains) attached to the ring nucieiwhichlowerwater solubility of the oil molecule; our'previously" described modes ofpracticeof' the instantinvention increase toxicity by; among otherthings, raisingthe specific gravity of aromatic andyor' overallfractions by what we believe to be. controlled side chain elimination;at least to a; degree, from the ring nuclei; However, we have discoveredthat when removing side chains from the ring nuclei which lower watersolubility, nascent radicles. are formed which may; on the one hand,further alkylatethe ring nuclei; or, on the other hand, polymerize toform high boiling chain structures which boilwithirr the range of thereformed aro mati-cs. In either instancethis is not desired, andmoreespecially the polymerization of the nascent radicles to formrelatively high boiling chain structures-isnot desired for the reasonthat they dilutethe toxicity ofthe reformed aromatics".

We have discovered that if wewill' remove side from the ring nucleiwithin a; relatively short period andtherrsheck cool the entire bene--ficiation; a. certain degree of the said polymerization and/oralkylation is precluded, thus resulting in a toxicity in the reformed,modified and /orconver-tedoil comparable tothat of high temperature coaltar oils.

When applying this mode of practice to our instant invention; wehold-the treating period to not in excess of twdhours; and preferablynot in excess' -ofabout 30-45 minutes. When employing relatively hightemperatures within the extreme upper liinits-ofthe range-previouslydisclosed, period'sof 15-30-minutes, or less; will sufllce forthenecessary reforming previously taught. Immediately thereafter thebeneficiation is shock cooled to s temperature below about 250 0., andpreferably-below 200 C; by a relatively cool oil; which may be thepreservative oilpreviously madeby the process. The reformed oil isfractioned as shown above.

Example 8i-A petroleum: aromatic, as for-example, the Shell oilpreviously described, is pumped in closed circuit through an apparatusdesigned-- to- Withstand high pressure and high temperature; 'I'hepressure is=maintained at 1000' pounds per square inch at atemperature of 480 C.- Theoil in the closed circuit is kept incirculation. At the end of about one hour or one hour and l5-minutes-,the heat treated oil is continuously withdrawn, with compensatingadmission of iresh" feed tothe circuit". The withdrawal and admissionare so regulated asto provide the heat treating period above named. Uponinspection of the withdrawn heat treated-material the percent age andspecific gravity of aromatics in the 210- 35596; cut Willi be found tofall within the limits previously disclosed The overall specific gravi--ti'es offractional parts of; the 2l0-355 C. out will alsobe -found t0fall within the limit previously shown; and the-toxicity-of the--overall 210-355" C. out will compare favorably with high temperaturecoal tar creosote.

In previous examples, the overall feed stock has been shown as beingtreated. In lieu of this, the raw feed stock may be divided into two ormore fractions and separately treated. As an example, the feed stock maybe divided into a relatively low boiling and relatively high boilingfraction. The low boiling fraction is then treated at a relatively hightemperature within the range disclosed, and the high boiling fraction istreated at a relatively low temperature within the range disclosed, theperiods of treatment in this instance being the same as taughtpreviously for high and low boiling cuts, beneficiated or otherwise. Ifthree cuts of the raw feed are made, the lowest boiling fraction istreated at the highest temperature, the intermediate fraction at anintermediate temperature and the highest boiling fraction at the lowesttemperature. This teaching applies to any number of cuts into which thefeed may be divided.

Viewed broadly, the product of the instant process is a reformed,modified and/or converted petroleum oil boiling preponderantly between210- 355 C., with at least about 15-20% material boiling above 315 0.,having at least about 70% aromatics in the materials boiling between 210C. and 355 C., and in the fractional parts of the oil boiling between2l0-355 C., certain specific gravities as taught in the foregoing.

The pressures in the present invention are in excess of atmospheric(with the possible exception of the second step of the mode of practicedescribed in Example 4) and may be as high as practicable, and thesepressures may be autogenous or arranged for by means well known in theart. 7

Either liquid or vapor phase may be practiced and this disclosure isspecifically to be read into all examples. Non-inventive skill willenable those acquainted with the art to coordinatetemperatures withinthe range disclosed with relatively moderate pressures in order toprovide vapor phase practice. When employing vapor phase operation andprocessing any of thefeed stocks previously described, definite periodsfalling within the limits previously disclosed will provide specificgravities and aromatic percentages shown in the foregoing.

One phase or various phases of one example may be substituted for aphase or various phases of another example where the substitution isobviously workable. g V

It is to be strictly understood that all temperatures, pressures andperiods of treatmentshown in the examples are for purposes ofillustration only.

Intermittent or continuous operation, or a combination thereof, may bepracticed in the instant process, and those skilled in the art can applythis to our invention without recourse to inventive skill.

Any theories or beliefs herein stated are not necessarily controlling;our invention being limited only by the scope of the appended claims,

Minor changes Within the scope of the appended claims may be madewithout departing from the spirit of the invention.

We claim:

1. In the induction of toxicity to wood destroying fungi into a mixtureof petroleum fractions boiling preponderantly above 270 0.,characterized by inherent but inhibited toxicity and a substantialpercentage of materials of ring structure content, the process whichcomprises: subjecting said material at superatmospheric pressure to atemperature selected between the limits of about 325-550 C. unveilingtoxicity in the material under treatment by carrying on the process fora period not substantially in excess of about two hours, the periodbeing so selected with reference to the chosen temperature and pressureas to jointly provide in the beneficiation newly formed materialsboiling below 210 C., a percentage of aromatics in the fractions boilingbetween 210- 355 C. not substantially less than about and a specificgravity in the aromatics above named falling between the limits shown inthe appended tabular data:

Fractions Low Limit High Limit whereby to provide a material of inducedtoxic properties.

2. i'he process of claim 1 with inclusion of segregating from thebeneficiated material an oil of the wood preservative type characterizedby induced toxic properties, boiling preponderantly between about210-355 C. and having at least 15-20% residual materials boiling above315 C.

3. In the induction of toxicity to wood destroying fungi into a mixtureof petroleum fractions boiling preponderantly above 270 0.,characterized by inherent but inhibited toxicity and a substantialpercentage of materials of ring structure content, the process whichcomprises: partially unveiling toxicity in the named materials bysubjecting same at superatmospheric pressure to a temperature selectedbetween the limits of about 325-550 C. whereby to provide an overallbeneficiation having relatively high and low toxicity in the materialsboiling below and above 270 C., respectively; segregating all of thematerials of relatively low toxicity boiling above 270 C. and subjectingsame at superatmospheric pressure to a temperature selected between thelimits above named; unveiling toxicity in a relatively high degree inthe materials under treatment by carrying on the process in both stepsof treatment for periods totalling not in excess of about two hours, theperiods being so selected with reference to the chosen temperatures andpressures as to provide newly formed materials boiling below 210 C., apercentage of aromatics in the fractions boiling between 2l0-355 C. notsubstantially less than 70%, and a specific gravity in the aromaticsabove named falling between the limits shown in the appended tabulardata:

Fractions Low Limit High Limit whereby to provide materials of inducedtoxic properties; and commingling the segregations above named wherebyto provide an overall oil of induced toxic properties which containsfractions essential in an acceptable preservative impregnant.

4. The process of claim 3 with inclusion of segregating from thebeneficiated material an oil of the wood preservative type characterizedby 13 induced toxic properties, boiling preponderantly between about 210C. and 355 C. and having at least about 15-20% residual materialsboiling above 315 C.

5. In the induction of toxicity to wood destroying fungi into a mixtureof petroleum fractions boiling preponderantly above 270 0.,characterized by inherent but inhibited toxicity and a substantialpercentage of materials of ring structure content, the process whichcomprises: subjecting said material at a relatively high pressure to atemperature selected between the limits of about 325-550 C. for a periodnot in excess of about one hour; thereafter subjecting the heat treatedmaterial substantially in entirety to a relatively low pressure withouta substantial reduction in temperature for a period not in excess ofabout 30 minutes; unveiling toxicity to a relatively high degree in thematerial under treatment by carrying on the two-stage process forperiods falling within the limits above named, the periods being soselected with reference to the chosen temperature and pressure as tojointly provide newly formed materials boiling below 210 C., apercentage of aromatics in the fractions boiling between 210-355" C. notsubstantially less than about 70%, and a specific gravity in thearomatics above named falling between the limits shown in the appendedtabular data:

whereby to provide a material of induced toxic properties.

6. The process of claim with inclusion of segregating from thebeneficiated material an oil of the wood preservative type characterizedby induced toxic properties, having at least about 15-20% residualmaterial boiling above 315 C., and boiling preponderantiy between about210 C. and 355 C.

7. In the induction of toxicity to wood destroying fungi into a mixtureof petroleum fractions boiling preponderantly above 270 C.,characterized by inherent but inhibited toxicity and a substantialpercentage of materials of ring structure content, the process whichcomprises: subjecting said material at superatmospheric pressure to arelatively low temperature selected between the limits of about 325-550C. for a period not in excess of about one hour; thereafter subjectingthe heat treated material substantially in entirety at superatmosphericpressure to a relatively high temperature for a period not substantiallyin excess of about one hour; unveiling toxicity to a relatively highdegree in the material under treatment by carrying on the two-stageprocess for periods falling within the limits above named, the periodsbeing so selected with reference to the chosen temperatures andpressures in the two steps as to jointly provide newly formed materialsboiling below 210 C., a percentage of aromatics in the fractions boilingbetween 210-355 C. not substantially less than about 70%, and a specificgravity in the aromatics 14 above named falling between the limits shownin the appended tabular data:

properties.

8. The process of claim 7 with inclusion of segregating from thebeneficiated material an oil of the wood preservative type characterizedby induced toxic properties, boiling preponderantly between 210 C. and355 C., and having at least about 15-20% residual materials boilingabove 315 C.

9. In the induction of toxicity to wood destroying fungi into a mixtureof petroleum fractions boiling preponderantly above 270 0.,characterized by inherent but inhibited toxicity and a substantialpercentage of materials of ring structure content, the process whichcomprises: subjecting said material at superatmospheric pressure to atemperature selected between the limits of about 325-550 C.; unveilingtoxicity in the material under treatment by carrying on the process fora period not in excess of about one hour, the period being so selectedwith reference to the chosen temperature and pressure as to jointlyprovide newly formed materials boiling below 210 C., a percentage ofaromatics in the fractions boiling between 210-355 C. not substantiallyless than about and a specific gravity in the aromatics above namedfalling between the limits shown in the appended tabular data:

Fractions Low Limit High Limit 210235 C 0. 9419 1. 0430 235270 0-- -1 1.0061 1. 0006 270-315 U 1. 0360 1. 0933 315-355" C 1. 0913 1. 1285whereby to provide a material of induced toxic properties; andprotecting the induced toxicity by shock quenching the overallbeneficiation.

JACQUELIN E. HARVEY, JR. ROBERT H. WHITE, JR. JOSEPH A. VAUGHAN.

REFERENCES CITED The following references are of record in the file ofthis patent:

UNITED STATES PATENTS

